Method of hydrodechlorination to produce dihydrofluorinated olefins

ABSTRACT

Disclosed herein is a process for the preparation of fluorine-containing olefins comprising contacting a chlorofluoroalkene with hydrogen in the presence of a catalyst at a temperature sufficient to cause replacement of the chlorine substituents with hydrogen. Also disclosed is a catalyst composition for the hydrodechlorination of chlorofluoroalkenes comprising copper metal deposited on a support.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a continuation of U.S. Ser. application No.12/147,644, filed Jun. 27, 2008, which claims the benefit of priority ofU.S. Provisional Applications 60/958,190, filed Jul. 3, 2007, and61/004,518, filed Nov. 27, 2007.

BACKGROUND INFORMATION

1. Field of the Disclosure

This disclosure relates in general to methods of synthesis offluorinated olefins.

2. Description of the Related Art

The fluorocarbon industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for manyapplications has been the commercialization of hydrofluorocarbon (HFC)compounds for use as refrigerants, solvents, fire extinguishing agents,blowing agents and propellants. These new compounds, such as HFCrefrigerants, HFC-134a and HFC-125 being the most widely used at thistime, have zero ozone depletion potential and thus are not affected bythe current regulatory phase-out as a result of the Montreal Protocol.

In addition to ozone depleting concerns, global warming is anotherenvironmental concern in many of these applications. Thus, there is aneed for compositions that meet both low ozone depletion standards aswell as having low global warming potentials. Certain hydrofluoroolefinsare believed to meet both goals. Thus there is a need for manufacturingprocesses that provide halogenated hydrocarbons and fluoroolefins thatcontain no chlorine that also have a low global warming potential.

SUMMARY

Disclosed is a process for the preparation of fluorine-containingolefins comprising contacting a chlorofluoroalkene with hydrogen in thepresence of a catalyst at a temperature sufficient to cause replacementof the chlorine substituents of the chlorofluoroalkene with hydrogen toproduce a fluorine-containing olefin. Also disclosed are catalystcompositions for the hydrodechlorination of chlorofluoroalkenescomprising copper metal deposited on a support, and comprising palladiumdeposited on calcium fluoride, poisoned with lead.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

DETAILED DESCRIPTION

Disclosed is a process for the preparation of fluorine-containingolefins comprising contacting a chlorofluoroalkene with hydrogen in thepresence of a catalyst at a temperature sufficient to cause replacementof the chlorine substituents of the chlorofluoroalkene with hydrogen toproduce a fluorine-containing olefin. Also disclosed are catalystcompositions for the hydrodechlorination of chlorofluoroalkenescomprising copper metal deposited on a support, and comprising palladiumdeposited on calcium fluoride, poisoned with lead.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims.

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein the term chlorofluoroalkene refers to compounds of theformula R_(f)CCl═CClR_(f) wherein each R_(f) is a perfluoroalkyl groupindependently selected from the group consisting of CF₃, C₂F₅, n-C₃F₇,i-C₃F₇, n-C₄F₉, i-C₄F₉ and t-C₄F₉, and wherein one of the R_(f) groupsmay be F. As used herein, the chlorofluoroalkenes referred to may beeither the E-stereoisomer, the Z-stereoisomer, or any mixture thereof.

As used herein, the term fluorine-containing olefin refers to compoundsof formula E- or Z-R¹CH═CHR², wherein each of R¹ and R² are,perfluoroalkyl groups independently selected from the group consistingof CF₃, C₂F₅, n-C₃F₇, i-C₃F₇, n-C₄F₉, i-C₄F₉ and t-C₄F₉, and wherein R²may be F.

As used herein, an alloy is a metal that is a combination of two or moreelements, at least one of which is a metal.

In one embodiment, the process is run in the presence of a catalyst.

Hydrogenation catalysts containing copper, nickel, chromium, palladium,and ruthenium are known in the art. They may be prepared by eitherprecipitation methods or impregnation methods as generally described bySatterfield on pages 87-112 in Heterogeneous Catalysis in IndustrialPractice, 2^(nd) edition (McGraw-Hill, New York, 1991).

In one embodiment, the catalyst for the process is selected from thegroup consisting of copper on carbon, copper on calcium fluoride,palladium on barium sulfate, palladium/barium chloride on alumina,Lindlar catalyst (palladium on CaCO₃, poisoned with lead), palladium oncalcium fluoride poisoned with lead, copper and nickel on carbon, nickelon carbon, nickel on calcium fluoride, copper/nickel/chromium on calciumfluoride and unsupported alloys of copper and nickel.

In another embodiment, the catalyst is selected from the groupconsisting of copper on carbon, copper on calcium fluoride, copper andnickel on carbon, nickel on carbon, copper/nickel/chromium on calciumfluoride and unsupported alloys of copper and nickel. In one embodiment,the amount of copper on carbon or calcium fluoride support is from about1 % by weight to about 25% by weight. The carbon support may be acidwashed carbon.

In one embodiment, the palladium on barium sulfate catalyst may containfrom about 0.05% to 10% by weight palladium. In one embodiment, copperand nickel on carbon may contain from about 1% to about 25% by weightcopper and nickel combined on the carbon support.

The carbon support may be any of the carbon supports as describedpreviously herein for other catalysts. The weight ratio of the copper tonickel in the copper and nickel on carbon catalyst may range from about2:1 to about 1:2.

In one embodiment, the palladium/barium chloride on alumina catalyst maycontain from about 1 % to about 25% by weight barium chloride and fromabout 0.05% to about 10% by weight palladium relative to the totalweight of the catalyst composition. Preparation of a palladium/bariumchloride on alumina catalyst is described in U.S. Pat. No. 5,243,103,the disclosure of which is herein incorporated by reference.

In one embodiment, the palladium on calcium fluoride catalyst poisonedwith lead may contain from about 0.02% to about 5% palladium by weight.In one embodiment, in the preparation of the palladium on calciumfluoride poisoned with lead catalyst, the ratio of lead acetate insolution to palladium on support is from about 0.5:1 to about 2:1.

In one embodiment, the molar ratio of copper:nickel:chromium oxide inthe copper/nickel/chromium on calcium fluoride catalyst is from about 0to about 1 copper, from about 0.5 to about 3.0 nickel, and from about 0to about 2 chromium. In one embodiment, the molar ratio ofcopper:nickel:chromium in the copper/nickel/chromium on calcium fluoridecatalyst is 1.0:1.0:1.0. In another embodiment, the molar ratio is1.0:2.0:1.0. In yet another embodiment, the molar ratio is 1.0:2.0:0.25.In yet another embodiment, the molar ratio is 0.5:3.0:0.5. In yetanother embodiment, the molar ratio is 0.5:0.5:2.0. In yet anotherembodiment, the molar ratio is 0:3.0:1.0. In yet another embodiment, themolar ratio is 1:3.0:0. In one embodiment, the weight ratio of totalcatalyst material to support material may be from about 1:2 to about2:1. A method of preparation of the copper/nickel/chrome catalyst isdescribed in U.S. Pat. No. 2,900,423, the disclosure of which is hereinincorporated by reference.

In one embodiment, the unsupported alloys of copper and nickel includethose described by Boudart in Journal of Catalysis, 81, 204-13, 1983,the disclosure of which is herein incorporated by reference. In oneembodiment, the mole ratio of Cu:Ni in the catalysts may range fromabout 1:99 to about 99:1. In another embodiment, the mole ratio of Cu:Niis about 1:1.

In one embodiment, the contact time for the process ranges from about 2to about 120 seconds.

In one embodiment, the ratio of hydrogen to chlorofluoroalkene is fromabout 1:1 to about 7.5:1. In another embodiment, the ratio of hydrogento chlorofluoroalkene is from about 1:1 to about 5:1. In anotherembodiment, the ratio of hydrogen to chlorofluoroalkene is from about5:1 to about 10:1.

In one embodiment, the process for preparation of fluorine-containingolefins comprises reacting a chlorofluoroalkene with hydrogen in areaction vessel constructed of an acid resistant alloy material. Suchacid resistant alloy materials include stainless steels, high nickelalloys, such as Monel, Hastelloy, and Inconel. In one embodiment, thereaction takes place in the vapor phase.

In one embodiment, the temperature at which the process is run may be atemperature sufficient to cause replacement of the chlorine substituentswith hydrogen. In another embodiment, the process is conducted at atemperature of from about 100° C. to about 450° C.

In some embodiments, the pressure for the hydrodechlorination reactionis not critical. In other embodiments, the process is performed atatmospheric or autogenous pressure. Means may be provided for theventing of the excess pressure of hydrogen chloride formed in thereaction and may offer an advantage in minimizing the formation of sideproducts.

Additional products of the reaction may include partiallyhydrodechlorinated intermediates; saturated hydrogenated compounds;various partially chlorinated intermediates or saturated compounds; andhydrogen chloride (HCl). For example, wherein the chlorofluoroalkene is2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (CFC-1316mxx, E- and/orZ-isomers), the compounds formed in addition to E- and/orZ-1,1,1,4,4,4-hexafluoro-2-butene (E- and/or Z-HFC-1336mzz) may include,1,1,1,4,4,4-hexafluorobutane (HFC-356mff), pentafluorobutane (HFC-1345,different isomers), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf),E and/or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E- and/orZ-HCFC-1326mxz), and 1,1,1,4,4,4-hexafluoro-2-butyne (HFB).

In certain embodiments, the present disclosure provides a catalystcomposition for the hydrodechlorination of chlorofluoroalkenescomprising copper metal deposited on a support.

In one embodiment, the catalyst composition for the hydrodechlorinationof chlorofluoroalkenes comprises copper metal deposited on a supportcomprising acid-washed carbon or calcium fluoride.

In one embodiment, the catalyst composition for the hydrodechlorinationof chlorofluoroalkenes comprises copper metal deposited on a supportwherein said copper metal comprises about 5% to about 25% by weight ofthe catalyst composition.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

In the examples the follow abbreviations or codes may be used:

-   CT=contact time-   t-1336=E-1336mzz=E-CF₃CH═CHCF₃-   c-1336=Z-1336mzz=Z-CF₃CH═CHCF₃-   356mff=CF₃CH₂CH₂CF₃-   1345=C₄H₃F₅-   346mdf=CF₃CHClCH₂CF₃-   1326=E- and/or Z-CF₃CH═CClCF₃-   t-1326mxz=Z-1326mxz=Z-CF₃CH═CClCF₃-   c-1326mxz=E-1326 mxz=E-CF₃CH═CClCF₃-   1316mxx=E/Z-CF₃CCl═CClCF₃-   t-1316mxx=E-1316mxx=E-CF₃CCl═CClCF₃-   c-1316mxx=Z-1316mxx=Z-CF₃CCl═CClCF₃-   171-14mccxx=E/Z-CF₃CF₂CF₂CCl═CClCF₂CF₂CF₃-   173-14mcczz=E/Z-CF₃CF₂CF₂CH═CHCF₂CF₂CF₃-   t-172-14=E-CF₃CF₂CF₂CCl═CHCF₂CF₂CF₃-   c-172-14=Z-CF₃CF₂CF₂CCl═CHCF₂CF₂CF₃-   HFB═CF₃C≡CCF₃

Example 1

Example 1 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overCu on carbon catalyst.

An Inconel® tube (⅝ inch OD) was filled with 13 cc (5.3 gm) of 25% Cu onacid washed carbon (18-30 mesh). The temperature of the reactor wasraised to 100° C. for 30 minutes under N₂ flow (30 sccm, 5.0×10⁻⁷m³/sec). The temperature was then increased to 250° C. under H₂ flow forone hour. The temperature and flows were changed as described in theexperiments in Table 1, below, and the reactor effluent was analyzed byGCMS to provide the following molar percent of products.

TABLE 1 Molar Temp CT ratio Reactor effluent concentration (molar %) °C. (sec) H₂/1316 t-1336 356mff 1345 c-1336 346mdf 1316mxx 1326 310 745.2:1 12 0 0 5 0 0 81 310 120 2.9:1 40 3 4 9 2 0 42 310 120 3.0:1 40 4 49 2 0 40 310 121 2.9:1 36 2 2 8 2 0 50 311 125 2.7:1 28 0 0 6 0 0 65 33974 5.1:1 36 2 2 10 2 0 47 340 97 3.4:1 48 3 5 12 0 0 33 340 100 3.4:1 463 3 11 2 0 36 340 68 5.3:1 40 2 4 12 2 0 40 340 73 4.8:1 29 1 2 11 0 057 340 123 2.4:1 52 3 3 11 0 0 30 340 71 5.4:1 39 2 4 11 2 0 42 340 1182.6:1 52 3 5 11 0 0 27

Example 2

Example 2 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overPd/BaCl₂/Al₂O₃ catalyst.

A Hastelloy reactor 10″ L ×½″ o.d.×0.034″ wall was filled with 11 cc ofthe catalyst. The catalyst was conditioned at 150° C. for 65 hrs inhydrogen flow of 50 sccm (8.3×10⁻⁷ m³/sec). Then the temperature wasraised to 300° C. for 2 hrs at the same flow. The hydrodechlorination of1316mxx was studied at temperatures of 240-400° C. as indicated in Table2. Products of the reaction were analyzed by GCMS to give the followingmolar concentrations.

TABLE 2 Molar ratio Reactor effluent concentration (molar %) Temp CT H₂/t- c- t- c- t- c- deg C. (sec) 1316mxx 1316 1345 356mff 1336 1326mxz1326mxz 1316mxx 1316mxx 240 30 1:1 11.96 0.65 7.58 1.14 19.41 0.62 49.701.82 240 30 1:1 11.39 0.57 7.81 1.13 20.35 0.64 49.21 1.79 300 10 2:123.55 3.38 13.30 1.39 27.14 0.27 15.98 0.26 300 10 2:1 22.31 2.55 14.591.35 27.50 0.32 17.76 0.37 325 30 1:1 26.95 0.30 3.14 3.80 19.77 0.9938.91 3.06 325 30 1:1 24.08 0.30 2.63 4.92 18.51 1.00 42.39 3.31 350 301:1 23.51 1.72 6.66 7.15 22.53 0.80 29.95 2.17 400 30 1:1 17.66 1.432.40 1.19 15.65 1.01 47.46 7.84

Example 3

Example 3 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overPd/BaSO₄ catalyst.

A Hastelloy reactor 10″ L×½″ o.d.×0.034″ wall was filled with 11 cc(19.36 g) of the catalyst. The catalyst was conditioned at 300° C. for 2hrs in hydrogen flow of 50 sccm (8.3×10⁻⁷ m³/sec). Thehydrodechlorination of 1316mxx was studied at 100-200° C. as indicatedin Table 3, below. The mole ratio of hydrogen to 1316mxx was 1:1.Contact time for all runs in Table 3 was 60 seconds. Products of thereaction were analyzed by GCMS to give the following molarconcentrations.

TABLE 3 Reactor effluent concentration (molar %) Temp c- t- c- t- c- °C. t-1336 356mff 1336 1336mxz 346mdf 1326mxz 136mxx 1316mxx 200 10.6413.35 0.45 31.66 10.91 0.90 29.81 0.54 200 10.25 13.40 0.44 30.56 10.160.99 31.85 0.61

Example 4

Example 4 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overLindlar catalyst.

Lindlar catalyst (from Strem Chemicals, Inc., Newburyport, Mass., USA)was pelletized and sieved to 12/20 mesh. 25 g of the catalyst was loadedinto a Hastelloy reactor 10″ L×½″ o.d.×0.034″ wall thickness. Thecatalyst was conditioned at 300° C. for 2 hrs in hydrogen flow of 50sccm (8.3×10⁻⁷ m³/sec). The hydrodechlorination of 1316mxx was studiedat 200-250° C. The mole ratio of hydrogen:1316 was 2:1 and the contacttime was 45 seconds for all runs in Table 4. Products of the reactionwere analyzed by GCMS to give the following molar concentrations.

TABLE 4 Reactor effluent concentration (molar %) Temp t- c- t- c- ° C.t-1336 356mff c-1336 1326mxz 346mdf 1326mxz 1316mxx 1316mxx 200 6.177.64 19.74 25.29 0.28 0.29 38.00 1.20 200 3.39 4.04 14.07 20.34 0.290.53 53.90 2.31 250 2.33 1.03 49.75 7.70 0.00 0.66 33.03 2.82

Example 5

Example 5 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overCu on carbon catalyst.

In a 400 ml Pyrex beaker a solution of 10.73 g CuCl₂.2H₂O was preparedin 65 ml of 10% HCl in deionized water. 46.0 g of acid washed carbon(10/30 mesh) was added to the solution. The stiff slurry was allowed tostand at room temperature for 1 hr with occasional stirring. Then theslurry was dried at 110-120° C. under air overnight. After that thecatalyst was transferred into quartz tube which was purged with 500 sccm(8.3×10⁻⁶ m³/sec) N₂ at 25° C. for 15 min, then 100 sccm each He and H₂for 15 min. Then the catalyst was heated at 5° C./min to 500° C. for 6hrs in He/H₂. The procedure gave 48.52 g of catalyst.

A Hastelloy reactor 10″ L×½″ o.d.×0.034″ wall was filled with 11 cc(4.73 g) of 8% Cu on acid washed carbon catalyst. The catalyst wasconditioned at 150° C. for 16 hrs in hydrogen flow of 50 sccm (8.3×10⁻⁷m³/sec). The temperature was raised to 350° C. for 2 hrs in hydrogenflow of 50 sccm (8.3×10⁻⁷ m³/sec). The hydrodechlorination of 1316mxxwas studied at temperatures ranging from about 300 to 400° C. asindicated in Table 5, below. Products of the reaction were analyzed byGCMS to give the following molar concentrations.

TABLE 5 Reactor effluent concentration (molar %) Molar Temp CT ratio t-c- t- c- t- t- ° C. (sec) H₂/1316 1336 1345 356mff 1336 1326mxz 1326mxz1316mxx 1316mxx 300 30 4:1 0.58 0.0 0.40 0.09 31.47 1.65 34.41 29.85 30060 4:1 1.65 0.0 1.18 0.12 73.93 4.16 5.16 11.72 340 60 4:1 27.34 0.060.90 1.38 66.35 2.87 0.0 0.0 340 75 5:1 56.81 1.18 3.42 3.25 32.00 1.140.0 0.0 325 75 5:1 35.80 0.66 2.62 2.63 53.64 2.05 0.0 0.0 360 75 5:168.83 2.54 5.14 3.21 17.76 0.63 0.0 0.0 360 75 5:1 66.08 2.63 5.27 3.3919.91 0.68 0.0 0.0 400 75 5:1 65.00 9.13 17.40 2.10 0.48 0.00 0.0 0.0400 50 5:1 69.78 5.93 8.94 4.39 7.07 0.08 0.0 0.0

Example 6

Example 6 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overCu on calcium fluoride catalyst.

A Hastelloy reactor 10″ L×½″ o.d.×0.034″ wall was filled with 10.5 cc(15.22 g) of 8% Cu on CaF₂ catalyst. The catalyst was conditioned at300° C. for 18 hrs in hydrogen flow of 50 sccm (8.3×10⁻⁷ m³/sec). Thehydrodechlorination of 1316mxx was studied at a temperature range of250-450° C. as indicated in Table 6, below. The contact time was 45seconds and the mole ratio of hydrogen:1316 was 5:1 for all runs inTable 6. Products of the reaction were analyzed by GCMS to give thefollowing molar concentrations.

TABLE 6 Reactor effluent concentration (molar %) Temp t- c- t- c- ° C.HFB t-1336 356mff c-1336 1326mxz 1326mxz 1316mxx 1316mxx 250 0.32 0.210.43 0.68 0.72 0.12 87.73 9.21 250 0.27 0.21 0.38 0.59 0.71 0.12 87.659.49 300 0.86 0.14 0.24 0.28 0.92 0.19 87.01 9.66 300 0.95 0.16 0.310.15 1.04 0.21 87.14 9.48 400 8.04 0.16 0.22 0.11 1.77 0.42 75.64 12.98450 3.36 0.13 0.19 0.09 1.93 0.48 58.16 35.07

Example 7

Example 7 demonstrates the conversion of CFC-1316mxx to HFC-1336 overCu/Ni on carbon catalyst.

A Hastelloy reactor 15″ L×1″ o.d.×0.074″ wall was filled with 23 cc (8.7g) of 1% Cu/1% Ni on carbon catalyst. The catalyst was conditioned with50 sccm (8.3×10⁻⁷ m³/sec) of hydrogen flow according to the followingprotocol:1 hr at 50° C., followed by 1 hr at 100° C., followed by 1 hrat 150° C., followed by 1 hr at 200° C., followed by 1 hr at 250° C.,followed by 2 hr at 300° C., followed by a final 16 hrs at 200° C.

The hydrodechlorination of 1316mxx was studied over a temperature rangeof 200-375° C. Products of the reaction were analyzed by GCMS to givethe molar concentrations as listed in Table 7.

TABLE 7 Molar Reactor effluent concentration (molar %) Temp CT ratio t-c- t- c- ° C. (sec) H₂/1316 t-1336 c-1336 1326mxz 1326mxz 1316mxx1316mxx 200 75   5:1 0.14 0.47 40.50 1.24 51.34 5.38 300 75   5:1 7.100.61 87.28 3.91 0.08 0.12 300 75 7.5:1 34.31 4.04 58.68 1.64 0.00 0.00350 30 7.5:1 60.33 6.51 29.96 0.47 0.00 0.00 375 30 7.5:1 75.71 6.988.41 0.05 0.00 0.00

Example 8

Example 8 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overNi on carbon catalyst.

A Hastelloy reactor 15″ L×1″ o.d.×0.074″ wall was filled with 23 cc(10.58 g) of 8% Ni on carbon catalyst. The catalyst was conditioned at50 sccm (8.3×10⁻⁷ m³/sec) of hydrogen flow according to the followingprotocol: 1 hr at 50° C., followed by 1 hr at 100° C., followed by 1 hrat 150° C., followed by 1 hr at 200° C., followed by 1 hr at 250° C.,followed by 2 hrs at 300° C., and finally followed by 16hrs at 250° C.

The hydrodechlorination of 1316mxx was studied at a temperature range of250-375° C. Products of the reaction were analyzed by GCMS to give themolar concentrations as listed in Table 8.

TABLE 8 Molar Reactor effluent concentration (molar %) Temp CT ratio t-c- t- c- t- c- ° C. (sec) H₂/1316 HFB 1336 1345 356mff 1336 1326mxz1326mxz 1316mxx 1316mxx 250 30 7.5:1 0.00 0.30 0.0 0.08 1.53 12.01 0.6573.11 11.75 275 30 7.5:1 0.04 0.51 0.04 0.12 3.13 17.14 0.90 54.74 22.59300 30 7.5:1 0.13 1.24 0.08 0.19 5.65 27.44 1.32 36.19 26.62 325 307.5:1 0.39 3.71 0.15 0.28 8.84 44.78 2.13 20.05 18.01 350 30 7.5:1 1.0412.05 0.30 0.48 11.69 58.59 2.68 5.70 5.12 375 30 7.5:1 0.74 30.63 0.621.12 11.84 47.46 1.78 1.00 0.86 375 75 7.5:1 0.04 61.30 1.29 3.06 6.9721.86 0.39 0.00 0.00 375 75   4:1 0.19 49.61 0.59 1.17 8.05 34.63 1.020.13 0.12

Example 9

Example 9 demonstrates the conversion of CFC-1316mxx to HFC-1336mzz overNi on calcium fluoride catalyst.

In a 400 ml Pyrex beaker a solution of 5.698 g Ni(NO₃)₂.6H₂O wasprepared in 25 ml of deionized water. 21.76 g of CaF₂ (12/30 mesh,sintered) was added to the solution. 46.0 g of acid washed carbon (10/30mesh) was added to the solution. The mixture was placed on a warmhotplate and dried to a damp solid 150-160° C. under air overnight. Thenthe catalyst was placed in quartz tube which was purged with 500 sccm(8.3×10⁻⁶ m³/sec) N₂ at 25° C. for 30 min, then 100 sccm each of He andH₂ for 15 min. Then the catalyst was heated at 0.5° C./min to 350° C.for 12 hrs in He/H₂. After cooling in He/H₂, the sample was passivatedin 2% O₂.N₂ at room temperature for 30 min. 22.728 g of the catalyst wasmade.

A Hastelloy reactor 15″ L×1″ o.d.×0.074″ wall was filled with 23 cc(15.24 g) of 5% Ni on CaF₂ catalyst. The catalyst was conditioned at 50sccm (8.3×10⁻⁷ m³/sec) hydrogen flow according to the followingprotocol: 1 hr at 50° C., followed by 1 hr at 100° C., followed by 1 hrat 150° C., followed by 1 hr at 200° C., and finally followed by 16 hrat 250° C.

The hydrodechlorination of 1316mxx was studied at a temperature range of250-450° C. and the products indicated in Table 9, below. Contact timewas 75 seconds in all cases. The ratio of hydrogen to 1316mxx was 5:1 inall cases. Products of the reaction were analyzed by GCMS to give themolar concentrations as listed in Table 9.

TABLE 9 Reactor effluent concentration (molar %) Temp t- c- t- c- ° C.t-1336 1345 356mff c-1336 1326mxz 1326mxz 1316mxx 1316mxx 250 0.09 0.230.64 2.45 1.08 0.19 84.59 9.49 400 7.52 1.42 1.93 29.96 3.37 0.54 31.2013.76 450 12.37 1.40 3.54 35.69 3.07 0.41 14.26 12.00 450 2.49 0.34 0.8112.95 1.97 0.40 39.60 33.21

Example 10

Example 10 demonstrates the conversion of CFC-1316mxx to HFC-1336mzzover a Cu/Ni/Cr on calcium fluoride catalyst.

A Hastelloy reactor 10″ L×½″ o.d.×0.034″ wall was filled with 11 cc ofCu/Ni/Cr/CaF2 (with molar ratio of metals 1:1:1) catalyst made by theprocess described in U.S. Pat. No. 2,900,423. This catalyst was analyzedby X-Ray Fluorescence and found to contain (mole %) 61.0% F, 13.5% Ca,9.4% Cr, 6.9% Ni, and 6.1% Cu, and 3.0% K. The catalyst was conditionedat 250° C. for 90 hrs in hydrogen flow of 50 sccm (8.3×10⁻⁷ m³/sec). Thetemperature was raised to 400° C. for 2 hrs in hydrogen flow of 50 sccm(8.3×10⁻⁷ m³/sec). The hydrodechlorination of 1316mxx was studied at atemperature range of 350-450° C., as indicated by the results in Table10, below. For all runs in Table 10, the ratio of hydrogen:1316 was 2:1.Products of the reaction were analyzed by GCMS to give the molarconcentrations as listed in table 10.

TABLE 10 Reactor effluent concentration (molar %) Temp CT t- c- t- c- t-c- ° C. (sec) HFB 1336 356mff 1336 1326mxz 1326mxz 1316mxx 1316mxx 35015 22.9 0.4 0.0 1.8 3.7 0.3 61.9 6.7 400 15 29.5 0.7 0.0 3.2 2.8 0.353.4 6.8 450 15 30.5 0.6 0.4 0.8 2.2 0.4 41.2 14.8 400 30 40.5 0.9 0.72.3 5.0 0.6 35.1 6.8 400 45 43.3 1.1 0.6 2.7 6.0 0.7 30.1 6.1 450 4553.1 4.5 0.4 10.7 6.1 0.5 8.5 3.9

Example 11

Example 11 demonstrates the conversion of CFC-1316mxx to HFC-1336mzzover a Cu/Ni/Cr on calcium fluoride catalyst.

A Hastelloy reactor 10″ L×½″ o.d.×0.034″ wall was filled with 11 cc ofCu/Ni/Cr/CaF2 (with molar ratio of metals 1:2:1) catalyst made by theprocess described in U.S. Pat. No. 2,900,423. The catalyst wasconditioned at 400° C. for 2 hrs in hydrogen flow of 50 sccm (8.3×10⁻⁷m³/sec). The hydrodechlorination of 1316mxx was studied at a temperaturerange of 350-450° C. Products of the reaction were analyzed by GCMS togive the molar concentrations as indicated by the results in Table 11,below.

TABLE 11 Molar Reactor effluent concentration (molar %) Temp CT Ratio c-t- c- t- c- ° C. (sec) H₂/1316 HFB t-1336 1336 1345 1326mxz 1326mxz1316mxx 1316mxx 350 30 2:1 16.91 2.77 22.22 6.90 16.96 2.25 19.55 1.60375 30 2:1 27.69 2.81 24.73 5.66 13.25 1.08 13.64 1.05 375 45 2:1 29.862.22 22.32 2.94 12.85 0.98 19.42 1.86 375 45 4:1 23.30 5.68 38.11 2.2516.84 0.85 6.68 0.70 375 45 6:1 4.51 1.69 47.19 2.4 6.89 0.42 26.09 3.16

Example 12

Example 12 demonstrates the preparation of an unsupported copper/nickelcatalyst.

115 g (0.48 mole) of Cu(NO₃)₂*4H₂O was dissolved in 250 ml of water.145.5 g (0.5 mole) of Ni(NO₃)₂*6H₂O was dissolved in 250 ml H₂O mixedtogether with the copper solution, and then added to 174 g (2.2 g) ofNH₄HCO₃ dissolved in 2 L H₂O. The resulting slurry was stirred for 1 hr,allowed to settled overnight and filtered (paper filter). Solids wereplaced in a beaker with 2 L of water, stirred and filtered again. Themixed carbonates were dried in vacuum at 90° C. for 24 hrs. Then, theywere crushed and calcined in air at 400° C. for 2 hrs, then, recrushed,placed into furnace and reduced in a regime as follows. The temperaturewas ramped from room temperature to 260° C. in He, The concentration ofH₂ was increased to pure H₂ over 4 hrs, after which the temperature wasincreased to 350° C. and reduction was carried out for 16 hrs. Thesamples were passivated by cooling to room temperature in flowing He,gradually increasing the concentration of O₂ in the He stream over 2hrs. 46 g of black powder was made. The powder was pressed andpelletized into 12-20 mesh size.

Example 13

Example 13 illustrates the conversion of CFC-1316mxx to HFC-1336mzz overthe catalyst of example 12.

A Hastelloy reactor 15″ L×1″ o.d.×0.074″ wall was filled with 10 cc (25g) of Cu/Ni catalyst. The catalyst was conditioned at 50 sccm (8.3×10⁻⁷m³/sec) hydrogen flow at 350° C. The hydrodechlorination of 1316mxx wasstudied at a temperature range of 250-325° C. and the products indicatedin Table, below. Contact time was 15-60 seconds. The ratio of hydrogento 1316mxx was 5:1 or 7:1. Products of the reaction were analyzed byGCMS to give the molar concentrations as listed in Table 12.

TABLE 12 Contact H2/1316 Time, Temp t- c- t- t- c- ratio sec ° C. 13361345 356mff 1336 1326mxz 1316mxx 1316mxx 5:1 30 250 0.09 0.47 0.15 5.71.4 54.75 35.98 5:1 30 300 0.54 1.28 0.49 21.56 3.41 44.24 24.98 5:1 30325 1.04 2.13 2.13 33 4.04 36.39 17.41 7:1 30 325 1 2.23 0.65 39.2 3.1832.46 17.36 5:1 45 325 0.88 1.54 0.51 34.28 3.66 35.2 20.39 5:1 60 325 11.96 062 42.78 4.46 30.27 15.24 5:1 15 325 0.5 0.8 0.27 24.26 1.41 4328.14

Example 14

Example 14 illustrates the conversion of 4,5-dichloroperfluoro-4-octene(CFC-171-14mccx) to 4,5-dihydroperfluoro-4-octene (173-14mccz) overCu:Ni:Cr (0.5:0.48:0.02) catalyst.

An Inconel® tube (⅝ inch OD) was filled with 11 cc of Cu:Ni:Cr catalyst(12-20 mesh). The catalyst was activated at 350° C. for 2 hours under H₂flow. 4,5-Dichloroperfluoro-4-octene was evaporated at 200° C., and fedto the reactor at a flow rate of 1 mL/hour. The reaction was run at 300°C. Table 13 below shows contact time and hydrogen to 171-14 ratio, andthe composition of the reactor effluent as analyzed by GCMS to providethe following molar percent of products.

TABLE 13 Temp Contact Molar ratio c- t- c- ° C. time (sec) H₂:171-14173-14 172-14 172-14 t-171-14 300 30 10:1 53.1 5.2 7.7 22.6

Example 15

In a 400 ml Teflon beaker, a solution of 3.33 g PdCl₂ (60% Pd) in 100 ml10% HCl/H₂O was made. 98 g of CaF₂ was added to the beaker. The slurrywas allowed to stand at RT for 1 Hr with occasional stirring and thendried at 110° C. with occasional stirring. The dried solid was crushedto a powder and the powder was reduced at 300° C. in a He—H₂ flow for 8hrs. The initial gas composition forth reduction is 10% H₂, increasingto 100% over 4 hours. Then 2.45 g of lead acetate was dissolved in 100ml of water. To the beaker with the lead acetate solution 99.3 g of 2%Pd/CaF₂ was added. The slurry was stirred at 50° C. for 2 hrs. The solidwas collected on filter paper and dried at 110° C. for 16 hrs. Thecatalyst was pressed and pelletized to 12-20 mesh size.

Example 16

A Hastelloy reactor 15″ L×1″ o.d.×0.074″ wall was filled with 5 cc ofthe catalyst of Example 15. The catalyst was conditioned at 50 sccm(8.3×10⁻⁷ m³/sec) hydrogen flow at 250° C. The hydrodechlorination of1316mxx was studied over a temperature range of 200-300° C. and theproducts indicated in Table 14, below. Contact time was from 2.5 to 30seconds. The ratio of hydrogen to 1316mxx was from 2:1 to 6.3:1 asindicated. Products of the reaction were analyzed by GCMS to give themolar concentrations as listed in Table 14.

TABLE 14 Contact H2/1316 Time, Temp t- t- c- ratio sec ° C. t-1336356mff c-1336 1326mxz 346mdf 1316mxx 1316mxx 2:1 30 200 4.78 9.26 13.2211.46 2.32 37.35 16.17 2:1 30 250 14.96 16.21 17.97 25.4 3.21 17.22 2.652:1 4 250 2.66 2.85 13.03 8.91 1.14 41.28 23.37 4:1 2.5 250 2.79 3.5913.52 8.96 1.42 40.54 22.56 6.3:1   2.5 200 2.92 5.65 12.57 12.83 1.7347.16 13.65 6.3:1   2.5 250 6.68 8.11 23.58 21.26 1.32 31.64 5.39

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, any reference to values stated in ranges includes each andevery value within that range.

1. A process for the preparation of fluorine-containing alkynes comprising contacting a chlorofluoroalkene with hydrogen in the gas phase in the presence of a catalyst at a temperature sufficient to cause elimination of the chlorine substituents of the chlorofluoroalkene to produce a fluorine-containing alkyne, wherein said catalyst is a composition comprising copper, nickel and.chromium.
 2. The process of claim 1 wherein said catalyst is supported on calcium fluoride.
 3. The process of claim 2 wherein the molar ratio of copper:nickel:chromium in the copper/nickel/chromium on calcium fluoride catalyst is 1 copper:about 1 to about 6 nickel, and about 0.25 to about 4 chromium.
 4. The process of claim 1 wherein the chlorofluoroalkene has the formula R_(f)CCl═CClR_(f) wherein each R_(f) is a perfluoroalkyl group independently selected from the group consisting of CF₃, C₂F₅, n-C₃F₇, i-C₃F₇, n-C₄F₉, i-C₄F₉ and t-C₄F₉, and wherein one of the R_(f) groups may be F.
 5. The process of claim 4 wherein each R_(f) is CF₃.
 6. The process of claim 1 wherein the fluorine-containing alkyne has the formula R¹CH═CHR², wherein each of R¹ and R² are, perfluoroalkyl groups independently selected from the group consisting of CF₃, C₂F₅, n-C₃F₇, i-C₃F₇, n-C₄F₉, i-C₄F₉ and t-C₄F₉, and wherein R² may be F.
 7. The process of claim 6 wherein each of R¹ and R² is CF₃.
 8. The process of claim 1 wherein the process is conducted at a temperature of from about 350° C. to about 450° C.
 9. The process of claim 1 wherein the ratio of hydrogen to chlorofluoroalkene is from about 2:1 to about 6:1.
 10. The process of claim 1 wherein the ratio of hydrogen to chlorofluoroalkene is from about 2:1 to about 4:1.
 11. The process of claim 1 wherein the ratio of hydrogen to chlorofluoroalkene is about 2:1.
 12. The process of claim 2 wherein the molar ratio of copper:nickel:chromium in the copper/nickel/chromium on calcium fluoride catalyst is 1 copper:about 1 to about 3.0 nickel, and about 0.25 to about 1 chromium.
 13. The process of claim 2 wherein the molar ratio of copper:nickel:chromium in the copper/nickel/chromium on calcium fluoride catalyst is 1 copper:about 1 to about 2 nickel, and about 0.5 to about 1 chromium. 